Oxymethoxy-3-aryl-pyrone derivatives

ABSTRACT

The invention relates to novel oxymethoxy-3-aryl-pyrone derivatives of the formula (I)                    
     in which 
     A, D, R 1 , R 2 , X, Y, Z and n have the meanings specified in the description, a process for their preparation and their use as pesticides, fungicides and herbicides.

This application is a divisional of application Ser. No. 09/077,237,filed on May 22, 1998 (now U.S. Pat No. 6,071,937, issued Jun. 6, 2000which is a 371 PCT/EP96/05058 filed Nov. 18, 1996).

The invention relates to novel oxymethoxy-3-aryl-pyrone derivatives, aprocess for their preparation and their use as pesticides, fungicidesand herbicides.

Certain phenyl-pyrone derivatives which are unsubstituted in the phenylring have already been disclosed (cf. A. M. Chirazi, T. Kappe and E.Ziegler, Arch. Pharm. 309, 558 (1976) and K.-H. Boltze and K.Heidenbluth, Chem. Ber. 91, 2849 (1958)), no possible use as pesticidesbeing specified for these compounds. Phenyl-ring-substitutedphenyl-pyrone derivatives having herbicidal, acaricidal and insecticidalproperties are described in EP-A-588 137.

However, the activity and spectrum of activity of these compounds is notalways completely satisfactory, in particular at low application ratesand concentrations. In addition, the tolerance by plants is frequentlyinadequate.

Novel compounds of the formula (I)

have now been found,

in which

X represents halogen, nitro, cyano, alkyl, alkenyl, alkoxy, alkenyloxy,alkylthio, alkylsulfinyl, alkylsulfonyl, halogenoalkyl, halogenoalkenyl,halogenoalkoxy, halogenoalkenyloxy or in each case unsubstituted orsubstituted phenyl, phenoxy, phenylthio, benzyloxy or benzylthio,

Y represents hydrogen, halogen, nitro, cyano, alkyl, alkenyl, alkoxy,alkenyloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, halogenoalkyl,halogenoalkenyl, halogenoalkoxy or halogenoalkenyloxy,

Z represents halogen, nitro, cyano, alkyl, alkenyl, alkoxy, alkenyloxy,halogenoalkyl, halogenoalkenyl, halogenoalkoxy or halogenoalkenyloxy,

n represents one of the numbers 0, 1, 2 or 3,

A represents hydrogen, halogen; an unsubstituted or substituted radicalselected from the group comprising alkyl, cycloalkyl, alkenyl, alkinyl,arylalkyl, aryl, hetarylalkyl or hetaryl; or one of the groups —COR³,—CO₂R³, —CN, —CONR³R⁴, —SO₂R³ or —P(O)(OR³)OR⁴, in which

R³ and R⁴ independently of one another represent hydrogen or in eachcase unsubstituted or substituted alkyl, alkenyl, arylalkyl, aryl,hetarylalkyl or hetaryl or

R³ and R⁴ together represent an unsubstituted or substituted alkylenegroup, in which one or more methylene groups is or are optionallyreplaced by the same number of hetero atoms,

D represents hydrogen or an unsubstituted or substituted radicalselected from the group comprising alkyl, alkenyl, alkinyl, alkoxyalkyl,polyalkoxyalkyl, alkylthioalkyl, saturated or unsaturated cycloalkyl,saturated or unsaturated heterocyclyl, arylalkyl, aryl, hetarylalkyl andhetaryl or

A and D together represent in each case an unsubstituted or substitutedalkylene or alkenylene group, in each of which one or more methylenegroups is or are optionally replaced by the same number of hetero atomsor hetero groups,

R¹ represents hydrogen or alkyl which is optionally substituted byhalogen and

R² represents alkyl, alkenyl or alkinyl, each of which is optionallysubstituted by halogen.

The compounds of the formula (I) can also be present, depending on thenature of the substituents, as geometric and/or optical isomers orisomer mixtures, in differing composition, which can optionally beseparated in a conventional manner. Both the pure isomers and the isomermixtures, and their preparation and use and compositions containingthese are subject-matter of the present invention.

However, for the sake of simplicity, compounds of the formula (I) willalways be referred to below, although both the pure compounds and,optionally, also mixtures having differing proportions of isomericcompounds are intended.

The compounds of the formula (I) can, depending on the position of theketo group, occur in the two isomeric forms of the formulae (I)_(a) and(I)_(b),

which is intended to be expressed by the dashed line in the formula (I).

The compounds of the formulae (I)_(a) and (I)_(b) can occur both asmixtures and in the form of their pure isomers. Mixtures of thecompounds of the formulae (I)_(a) and (I)_(b) may optionally beseparated by physical methods in a manner known per se, for example bychromatographic methods.

For reasons of increased clarity, only one of the possible isomers ineach case will be cited below. This includes the possibility of thecompounds, if appropriate, occurring in the form of the isomericmixtures or in the other respective isomeric form.

It has further been found that the novel compounds of the formula (I)

in which

A, D, X, Y, Z, R¹, R² and n have the meanings given above, are obtainedwhen compounds of the formula (II)

in which

A, D, X, Y, Z and n have the meanings given above,

are reacted with compounds of the formula (III)

in which

R¹ and R² have the meanings given above and

Hal represents halogen (preferably chlorine or bromine),

in the presence or absence of a diluent and in the presence or absenceof a reaction auxiliary.

It has further been found that the novel compounds of the formula (I),together with good tolerance by plants, have a very good activity aspesticides, preferably as insecticides and acaricides, but also againstparasites in animal husbandry. Furthermore, some of the novel compoundsof the formula (I) have very good microbicidal, preferably fungicidal,activity. Herbicidal activities were preferentially found at higherapplication rates.

The compounds according to the invention are generally defined by theformula (I). Preferred substituents or ranges of the radicals cited inthe formulae mentioned above and below are described below:

X preferably represents fluorine, chlorine, bromine, iodine, nitro,cyano, C₁-C₈-alkyl, C₂-C₆-alkenyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy,C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-alkylsulfonyl; C₁-C₆-alkyl,C₂-C₆-alkenyl, C₁-C₆-alkoxy or C₂-C₆-alkenyloxy, each of which issubstituted by fluorine, chlorine or bromine; or phenyl, phenoxy,phenylthio, benzyloxy or benzylthio, each of which is optionallysubstituted by fluorine, chlorine, bromine, iodine, nitro, cyano or byC₁-C₆-alkyl or C₁-C₆-alkoxy, each of which is optionally substituted byfluorine, chlorine or bromine.

Y preferably represents hydrogen, fluorine, chlorine, bromine, iodine,nitro, cyano, C₁-C₈-alkyl, C₂-C₆-alkenyl, C₁-C₆-alkoxy,C₂-C₆-alkenyloxy, C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl,C₁-C₆-alkylsulfonyl; or C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₆-alkoxy orC₂-C₆-alkenyloxy, each of which is substituted by fluorine, chlorine orbromine.

Z preferably represents fluorine, chlorine, bromine, iodine, nitro,cyano, C₁-C₈-alkyl, C₂-C₆-alkenyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy; orC₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₆-alkoxy or C₂-C₆-alkenyloxy each ofwhich is substituted by fluorine, chlorine or bromine.

n preferably represents one of the numbers 0, 1, 2 or 3.

A preferably represents hydrogen, fluorine, chlorine, bromine or iodine;a radical selected from the group consisting of C₁-C₁₀-alkyl,C₃-C₁₀-cycloalkyl, C₃-C₁₀-alkenyl and C₃-C₁₀-alkinyl, which radical isoptionally substituted by fluorine, chlorine, bromine or iodine; aradical selected from the group consisting of phenyl, naphthyl, 5- or6-membered hetaryl having one to three hetero atoms selected from thegroup consisting of oxygen, sulfur and nitrogen, phenyl-C₁-C₆-alkyl and5- or 6-membered hetaryl-C₁-C₆-alkyl having one to three hetero atomsselected from the group consisting of oxygen, sulfur and nitrogen, whichradical is optionally substituted by fluorine, chlorine, bromine,iodine, nitro, C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkylthio,C₁-C₈-halogenoalkyl, C₁-C₈-halogenoalkoxy or cyano, or one of the groups—COR³, —CO₂R³, —CN, —CONR³R⁴, —SO₂R³ or —P(O)(OR³)OR⁴, in which

R³ and R⁴ independently of one another represent hydrogen; C₁-C₁₀-alkylor C₃-C₁₀-alkenyl, each of which is optionally substituted by fluorine,chlorine, bromine or iodine, or a radical selected from the groupconsisting of phenyl, naphthyl, 5- or 6-membered hetaryl having one tothree hetero atoms selected from the group consisting of oxygen, sulfurand nitrogen, phenyl-C₁-C₆-alkyl and 5- or 6-memberedhetaryl-C₁-C₆-alkyl having one to three hetero atoms selected from thegroup consisting of oxygen, sulfur and nitrogen, which radical isoptionally substituted by fluorine, chlorine, bromine, iodine, nitro,C₁-C₈-alkyl, C₁-C₈-alkoxy, C₁-C₈-alkylthio, C₁-C₈-halogenoalkyl,C₁-C₈-halogenoalkoxy or cyano, or

R³ and R⁴ together represent a C₂-C₇-alkylene group in which onenon-terminal methylene group is optionally replaced by oxygen, sulfur,NH or N—C₁-C₄-alkyl.

D preferably represents hydrogen; C₁-C₁₂-alkyl, C₃-C₈-alkenyl,C₃-C₈-alkinyl, C₁-C₁₀-alkoxy-C₂-C₈-alkyl, poly-C₁-C₈-alkoxy-C₂-C₈-alkylor C₁-C₁₀-alkylthio-C₂-C₈-alkyl, each of which is optionally substitutedby fluorine, chlorine, bromine or iodine; cyano-,C₁-C₈-alkyloxycarbonyl- or C₁-C₈-alkylcarbonyloxy-substitutedC₁-C₁₂-alkyl; C₃-C₈-cycloalkyl, which is optionally substituted byhalogen, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₄-halogenoalkyl and in whichone or two not directly adjacent methylene groups are optionallyreplaced by oxygen and/or sulfur; or phenyl, hetaryl having 5 to 6 ringatoms and one to three hetero atoms selected from the group consistingof oxygen, sulfur and nitrogen, phenyl-C₁-C₆-alkyl orhetaryl-C₁-C₆-alkyl having 5 to 6 ring atoms and one to three heteroatoms selected from the group consisting of oxygen, sulfur and nitrogen,each of which is optionally substituted by halogen, C₁-C₆-alkyl,C₁-C₆-halogenoalkyl, C₁-C₆-alkoxy, C₁-C₆-halogenoalkoxy, cyano or nitro,or

A and D together preferably represent a C₂-C₇-alkylene orC₂-C₇-alkenylene group, each of which is optionally substituted byC₁-C₈-alkyl, fluorine, chlorine, bromine or iodine and in which twocarbon atoms are optionally joined by a C₁-C₂-alkylene group and inwhich a methylene group is optionally replaced by oxygen, sulfur, NH,N—C₁-C₄-alkyl or the group —O—CO—.

R¹ preferably represents hydrogen or C₁-C₈-alkyl, which is optionallysubstituted by fluorine, chlorine, bromine or iodine.

R² preferably represents C₁-C₁₀-alkyl, C₃-C₁₀-alkenyl or C₃-C₁₀-alkinyl,each of which is optionally substituted by fluorine, chlorine, bromineor iodine.

X particularly preferably represents fluorine, chlorine, bromine, nitro,cyano, C₁-C₆-alkyl, C₂-C₄-alkenyl, C₁-C₄-alkoxy, C₂-C₄-alkenyloxy,C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl; C₁-C₄-alkyl,C₂-C₄-alkenyl, C₁-C₄-alkoxy or C₂-C₄-alkenyloxy, each of which issubstituted by fluorine or chlorine; or phenyl, phenoxy, phenylthio,benzyloxy or benzylthio, each of which is optionally substituted byfluorine, chlorine, bromine, nitro or cyano or by C₁-C₄-alkyl orC₁-C₄-alkoxy, each of which is optionally substituted by fluorine orchlorine.

Y particularly preferably represents hydrogen, fluorine, chlorine,bromine, nitro, cyano, C₁-C₆-alkyl, C₂-C₄-alkenyl, C₁-C₄-alkoxy,C₂-C₄-alkenyloxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl,C₁-C₄-alkylsulfonyl; or C₁-C₄-alkyl or C₁-C₄-alkoxy, each of which issubstituted by fluorine or chlorine.

Z particularly preferably represents fluorine, chlorine, bromine, nitro,cyano, C₁-C₆-alkyl, C₁-C₄-alkoxy, C₂-C₄-alkenyloxy; or C₁-C₄-alkyl orC₁-C₄-alkoxy, each of which is substituted by fluorine or chlorine.

n particularly preferably represents one of the numbers 0, 1 or 2.

A particularly preferably represents hydrogen, fluorine, chlorine orbromine; a radical selected from the group consisting of C₁-C₈-alkyl,C₃-C₈-cycloalkyl, C₃-C₈-alkenyl and C₃-C₈-alkinyl, which radical isoptionally substituted by fluorine, chlorine or bromine; a radicalselected from the group consisting of phenyl, naphthyl, furanyl,thienyl, pyridyl, phenyl-C₁-C₄-alkyl, furanyl-C₁-C₄-alkyl,thienyl-C₁-C₄-alkyl and pyridyl-C₁-C₄-alkyl, which radical is optionallysubstituted by fluorine, chlorine, bromine, nitro, C₁-C₄-alkyl,C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxyor cyano; or one of the groups —COR³, —CO₂R³, —CN, —CONR³R⁴, —SO₂R³ or—P(O)(OR³)OR⁴, in which

R³ and R⁴ independently of one another represent hydrogen; C₁-C₈-alkylor C₃-C₈-alkenyl, each of which is optionally substituted by fluorine,chlorine or bromine; or a radical selected from the group consisting ofphenyl, furanyl, thienyl, pyridyl, phenyl-C₁-C₄-alkyl,furanyl-C₁-C₄-alkyl, thienyl-C₁-C₄-alkyl and pyridyl-C₁-C₄-alkyl, whichradical is optionally substituted by fluorine, chlorine, bromine, nitro,C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-halogenoalkyl,C₁-C₄-halogenoalkoxy or cyano or

R³ and R⁴ together represent a C₂-C₆-alkylene group, in which anon-terminal methylene group is optionally replaced by oxygen, sulfur,NH or N—C₁-C₄-alkyl.

D particularly preferably represents hydrogen; C₁-C₁₀-alkyl,C₃-C₆-alkenyl, C₃-C₆-alkinyl, C₁-C₈-alkoxy-C₂-C₆-alkyl,poly-C₁-C₆-alkoxy-C₂-C₆-alkyl or C₁-C₈-alkylthio-C₂-C₆-alkyl, each ofwhich is optionally substituted by fluorine or chlorine; C₁-C₈-alkylwhich is substituted by cyano, C₁-C₆-alkoxycarbonyl orC₁-C₆-alkylcarbonyloxy; C₃-C₇-cycloalkyl which is optionally substitutedby fluorine, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₂-halogenoalkyl,and in which one or two non-directly adjacent methylene groups areoptionally replaced by oxygen and/or sulfur; or phenyl, furanyl,imidazolyl, pyridyl, thiazolyl, pyrazolyl, pyrimidyl, pyridazyl,pyrazinyl, pyrrolyl, thienyl, triazolyl or phenyl-C₁-C₄-alkyl, each ofwhich is optionally substituted by fluorine, chlorine, bromine,C₁-C₄-alkyl, C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy, C₁-C₄-halogenoalkoxy,cyano or nitro, or

A and D together particularly preferably represent a C₂-C₆-alkylene orC₂-C₆-alkenylene group, each of which is optionally substituted byC₁-C₄-alkyl, fluorine, chlorine or bromine, in which two carbon atomsare optionally connected by a C₁-C₂-alkylene group and in which amethylene group is optionally replaced by oxygen, sulfur, NH,N—C₁-C₄-alkyl or the group —O—CO—.

R¹ particularly preferably represents hydrogen or C₁-C₄-alkyl which isoptionally substituted by fluorine, chlorine or bromine.

R² particularly preferably represents C₁-C₈-alkyl, C₃-C₈-alkenyl orC₃-C₈-alkinyl, each of which is optionally substituted by fluorine,chlorine or bromine.

X very particularly preferably represents fluorine, chlorine, bromine,nitro, cyano, methyl, ethyl, n- or i-propyl, n-, s-, i- or t-butyl,vinyl, allyl, methallyl, methoxy, ethoxy, n- or i-propoxy, allyloxy,methallyloxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy,trifluoroethoxy, methylthio, methylsulfinyl or methylsulfonyl.

Y very particularly preferably represents hydrogen, fluorine, chlorine,bromine, nitro, cyano, methyl, ethyl, n- or i-propyl, n-, s-, i- ort-butyl, methoxy, ethoxy, n- or i-propoxy, allyloxy, methallyloxy,trifluoromethyl, difluoromethoxy, trifluoromethoxy, trifluoroethoxy,methylthio, methylsulfinyl or methylsulfonyl.

Z very particularly preferably represents fluorine, chlorine, bromine,nitro, cyano, methyl, ethyl, n- or i-propyl, n-, s-, i- or t-butyl,methoxy, ethoxy, n- or i-propoxy, allyloxy, methallyloxy,trifluoromethyl, difluoromethoxy, trifluoromethoxy or trifluoroethoxy.

n very particularly preferably represents either of the numbers 0 or 1.

A very particularly preferably represents hydrogen, fluorine, chlorineor bromine; a radical selected from the group consisting of C₁-C₆-alkyl,C₃-C₆-cycloalkyl, C₃-C₆-alkenyl and C₃-C₆-alkinyl, which radical isoptionally substituted by fluorine or chlorine; phenyl, furanyl,pyridyl, thienyl or benzyl, each of which is optionally substituted byfluorine, chlorine, bromine, methyl, ethyl, n-propyl, iso-propyl,methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano or nitro; orone of the groups —COR³, —CO₂R³, —CN, —CONR³R⁴, —SO₂R³ or—P(O)(OR³)—OR⁴, in which

R³ and R⁴ independently of one another represent hydrogen; C₁-C₆-alkylor C₃-C₆-alkenyl, each of which is optionally substituted by fluorine orchlorine; or phenyl which is optionally substituted by fluorine,chlorine, bromine, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio,C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxy or cyano, or

R³ and R⁴ together represent one of the groups —(CH₂)₃—, —(CH₂)₄—,—(CH₂)₅—, —CH₂—CH(CH₃(CH₂)₂—, CH₂O—(CH₂)₂— and —CH₂S—(CH₂)₂—.

D very particularly preferably represents hydrogen; C₁-C₈-alkyl,C₃-C₄-alkenyl, C₃-C₄-alkinyl, C₁-C₆-alkoxy-C₂-C₄-alkyl,poly-C₁-C₄-alkoxy C₂-C₄-alkyl or C₁-C₄-alkylthio-C₂-C₄-alkyl, each ofwhich is optionally substituted by fluorine or chlorine; orC₃-C₆-cycloalkyl which is optionally substituted by fluorine, chlorine,methyl or ethyl and in which one or two non-directly adjacent methylenegroups are optionally replaced by oxygen and/or sulfur; or phenyl,furanyl, pyridyl, thienyl or benzyl, each of which is optionallysubstituted by fluorine, chlorine, bromine, methyl, ethyl, n-propyl,iso-propyl, methoxy, ethoxy, trifluoromethyl, trifluoromethoxy, cyano ornitro, or

A and D together very particularly preferable represent one of thegroups —(CH₂)₃, —(CH₂)₄, —(CH₂)₅—, —CH₂—CH(C₃)(CH₂)₂—, —CH₂O—(CH₂)₂,—CH₂S—)CH₂)₂— or

R¹ very particularly preferably represents hydrogen; or methyl or ethyl,each of which is optionally substituted by fluorine or chlorine.

R² very particularly preferably represents methyl, ethyl, n- ori-propyl, n-, i-, s- or t-butyl, allyl, methallyl, butenyl, propargyl orbutinyl, each of which is optionally substituted by fluorine orchlorine.

The general radical definitions or explanations listed above or listedin preferred ranges can be combined in any manner among one another,that is to say including between the respective ranges and preferredranges. They apply to the end products and also correspondingly to theprecursors and intermediates.

According to the invention, preference is given to the compounds of theformula (I) which contain a combination of the meanings listed above aspreferred.

According to the invention, particular preference is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as particularly preferred.

According to the invention, very particular preference is given to thecompounds of the formula (I) which contain a combination of the meaningslisted above as very particularly preferred.

Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenylcan each be straight-chain or branched, as far as is possible, includingin combination with hetero atoms, such as in alkoxy.

Radicals which may optionally be substituted can be monosubstituted orpolysubstituted, where the substituents can be identical or different inthe case of polysubstitution.

If, for example,5-fluoro-3-[4-(2-bromo-4,6-dimethyl-phenyl)-4-hydroxy-6-methyl]-2-pyroneand propargyloxychloromethane are used as starting materials, the courseof the process of the invention can be reproduced by the followingreaction diagram:

Some of the 4-hydroxy-2-pyrones of the formula (II) required as startingmaterials in the process of the invention are novel. They are describedin EP-A-588 137 or are subject-matter of a prior, as yet unpublished,application by the applicant (German patent application having the filenumber 195 40 080.1 of 27.10.1995).

The compounds of the formula (III) required as starting materials in theprocess of the invention are compounds which are commercial, generallyknown or can be synthesized by known processes.

The process of the invention is characterized in that compounds of theformula (II) are reacted with α-alkoxy halides of the formula (III) inthe presence or absence of a diluent and in the presence or absence of areaction auxiliary.

Diluents which can be used in the process of the invention are allsolvents which are inert to the halides. Those which can preferably beused are hydrocarbons, such as benzine, benzene, toluene, xylene andtetralin, in addition halogenated hydrocarbons, such as methylenechloride, chloroform, carbon tetrachloride, chlorobenzene ando-dichlorobenzene, in addition ketones, such as acetone and methylisopropyl ketone, furthermore ethers, such as diethyl ether,tetrahydrofuran and dioxane, furthermore carboxylic esters, such asethyl acetate, nitrites, such as acetonitrile, and also highly polarsolvents, such as dimethylformamide, dimethyl sulfoxide and sulfolane.If the stability to hydrolysis of the halide permits, the reaction canalso be carried out in the presence of water.

Reaction auxiliaries which are suitable in the reaction according to theprocess of the invention are, for example, all conventional acidacceptors. Those which can preferably be used are tertiary amines, suchas triethylamine, pyridine, diazabicyclooctane (DABCO),diazabicycloundecene (DBU), diazabicyclononene (DBN), Hünig base andN,N-dimethylaniline, in addition alkaline earth metal oxides, such asmagnesium oxide and calcium oxide, furthermore alkali metal carbonatesand alkaline earth metal carbonates, such as sodium carbonate, potassiumcarbonate and calcium carbonate and alkali metal hydroxides such assodium hydroxide and potassium hydroxide.

The reaction temperature can be varied within a relatively broad rangein the process of the invention. Generally, temperatures between −20° C.and +150° C. are employed, preferably between 0° C. and 100° C.

When the process of the invention is carried out, the starting materialof the formula (II) and the halide of the formula (III) are generallyeach used in approximately equivalent amounts. However, it is alsopossible to use the halide in a relatively great excess (up to 5 mol).

The reaction can be carried out at atmospheric pressure or underelevated pressure; atmospheric pressure is preferably employed. Thework-up is performed by conventional methods of organic chemistry. Theend products are preferably purified by crystallization, chromatographicpurification or by so-called “incipient distillation”, that is removalof the volatile constituents in vacuo.

The compounds according to the invention are suitable, with good croptolerance and favorable toxicity to warm-blooded animals, forcontrolling animal pests, preferably arthropods and nematodes, inparticular insects and arachnids, which are encountered in agriculture,in forestry, in the protection of stored products and of materials, andin the hygiene field. They are active against normally sensitive andresistant species and against all or some stages of development. Theabove-mentioned pests include:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber.

From the order of the Diplopoda, for example, Blaniulus guttulatus. Fromthe order of the Chilopoda, for example, Geophilus carpophagus andScutigera spec. From the order of the Symphyla, for example,Scutigerella immaculata. From the order of the Thysanura, for example,Lepisma saccharina. From the order of the Collembola, for example,Onychiurus armatus.

From the order of the Orthoptera, for example, Blatta orientalis,Periplaneta americana, Leucophaea maderae, Blattella germanica, Achetadomesticus, Gryllotalpa spp., Locusta migratoria migratorioides,Melanoplus differentialis and Schistocerca gregaria.

From the order of the Dermaptera, for example, Forficula auricularia.From the order of the Isoptera, for example, Reticulitermes spp. Fromthe order of the Anoplura, for example, Phylloxera vastatrix, Pemphigusspp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.From the order of the Mallophaga, for example, Trichodectes spp. andDamalinea spp. From the order of the Thysanoptera, for example,Hercinothrips femoralis and Thrips tabaci. From the order of theHeteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesmaquadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.

From the order of the Homoptera, for example, Aleurodes brassicae,Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicorynebrassicae, Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosomalanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp.,Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus,Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphaxstriatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotushederae, Pseudococcus spp. and Psylla spp.

From the order of the Lepidoptera, for example, Pectinophoragossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolietisblancardella, Hyponomeuta padella, Plutella maculipennis, Malacosomaneustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrixthurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltiaspp., Earias insulana, Heliothis spp., Spodoptera exigua, Mamestrabrassicae, Panolis flammea, Prodenia litura, Spodoptera spp.,Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyraustanubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana.

From the order of the Coleoptera, for example, Anobium punctatum,Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus,Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedoncochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachnavarivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp.,Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus,Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogodermaspp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp.,Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha,Amphimallon solstitialis and Costelytra zealandica.

From the order of the Hymenoptera, for example, Diprion spp., Hoplocampaspp., Lasius spp., Monomorium pharaonis and Vespa spp.

From the order of the Diptera, for example, Aedes spp., Anopheles spp.,Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphoraerythrocephala, Lucilia spp, Chrysomyia spp., Cuterebra spp.,Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp.,Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinellafrit, Phorbia spp., Pegomyla hyoscyami, Ceratitis capitata, Dacus oleaeand Tipula paludosa.

From the order of the Siphonaptera, for example, Xenopsylla cheopis andCeratophyllus spp.

From the order of the Arachnida, for example, Scorpio maurus andLatrodectus mactans.

From the order of the Acarina, for example, Acarus siro, Argas spp.,Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptrutaoleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalommaspp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.

The active compounds according to the invention are distinguished by ahigh insecticidal and acaricidal activity.

They can be employed particularly successfully to control insects whichare harmful to plants, such as, for example, against the larvae of themustard beetle (Phaedon cochleariae), against the caterpillars of thediamond-back moth (Plutella maculipennis), against the caterpillars ofthe owlet moth (Spodoptera frugiperda), against the larvae of the greenrice leafhopper (Nephotettix cincticeps), against peach aphids (Myzuspersicae) or against black bean aphids (Aphis fabae) and to controlarachnids (Acari) which are harmful to plants, for example against thecommon spider mite (Tetranychus urticae).

The active compounds according to the invention have a high microbicidalactivity and can be used in practice to control undesiredmicroorganisms. The active compounds are also suitable for use asfungicides.

Fungicidal agents are employed in crop protection for controllingPlasmo-diophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericidal agents are employed in crop protection for controllingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Non-limiting examples which may be mentioned of some pathogens causingfungal and bacterial diseases which come under the generic names listedabove are:

Xanthomonas species, such as, for example, Xanthomonas campestris pv.oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv.lachrymans;

Erwinia species, such as, for example, Erwinia amylovora;

Pythium species, such as, for example, Pythium ultimum;

Phytophthora species, such as, for example, Phytophthora infestans;

Pseudoperonospora species, such as, for example, Pseudoperonosporahumuli or Pseudoperonospora cubensis;

Plasmopara species, such as, for example, Plasmopara viticola;

Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as, for example, Peronospora pisi or P.brassicae;

Erysiphe species, such as, for example, Erysiphe graminis;

Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Venturia species, such as, for example, Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P.graminea (conidia form: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as, for example, Cochliobolus sativus(conidia form: Drechslera, syn: Helminthosporium);

Uromyces species, such as, for example, Uromyces appendiculatus;

Puccinia species, such as, for example, Puccinia recondita;

Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;

Tilletia species, such as, for example, Tilletia caries;

Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae;

Pellicularia species, such as, for example, Pellicularia sasakii;

Pyricularia species, such as, for example, Pyricularia oryzae;

Fusarium species, such as, for example, Fusarium culmorum;

Botrytis species, such as, for example, Botrytis cinerea,

Septoria species, such as, for example, Septoria nodorum;

Leptosphaeria species, such as, for example, Leptosphaeria nodorum;

Cercospora species, such as, for example, Cercospora canescens,

Alternaria species, such as, for example, Alternaria brassicae; andPseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The fact that the active compounds are well tolerated by plants at theconcentrations required for controlling plant diseases permits thetreatment of aerial parts of plants, of propagation stock and seeds, andof the soil.

In such treatments, the active compounds according to the invention areused particularly successfully for treating infestation by the fungusSphaerotheca fuliginea, the causative organism of apple scab (Venturiainaequalis) and the fungi Botrytis cinerea and Pyricularia oryzae and,in addition, Uncinula necator and Podosphaera leucotricha.

The active compounds according to the invention can furthermore be usedas defoliants, desiccants, haulm killers and, especially, asweedkillers. By weeds, in the broadest sense, there are to be understoodall plants which grow in locations where they are not wanted. Whetherthe substances according to the invention act as total or selectiveherbicides depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria,Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio,Arnaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum,Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala,Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis,Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.

Dicotyledon crops of the genera: Gossypium, Glycine, Beta, Daucus,Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana,Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.

Monocotvledon weeds of the genera: Echinochloa, Setaria, Panicum,Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus,Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis,Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea,Dactyloctenium, Agrostis, Alopecurus and Apera.

Monocotvledon crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena,Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

Depending on the concentration, the compounds are suitable for totalweed control, for example on industrial terrain and rail tracks, and onpaths and areas with or without tree stands. Equally, the compounds canbe employed for controlling weeds in perennial crops, for exampleforests, ornamental tree plantings, orchards, vineyards, citrus groves,nut orchards, banana plantations, coffee plantations, tea plantations,rubber plantations, oil palm plantations, cocoa plantations, soft fruitplantings and hopfields, in lawns, turf and pastures, and for selectiveweed control in annual crops.

The compounds of the formula (I) according to the invention are suitablefor controlling monocotyledon and dicotyledon weeds in monocotyledon anddicotyledon crops, both in pre-emergence and in post-emergencetreatments.

The active compounds can be converted into the customary formulations,such as solutions, emulsions, wettable powders, suspensions, powders,dusts, pastes, soluble powders, granules, suspoemulsion concentrates,natural and synthetic materials impregnated with active compound, andmicroencapsulations in polymeric substances.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is liquid solvents and/orsolid carriers, optionally with the use of surfactants, that isemulsifiers and/or dispersants and/or foam-formers.

If water is used as extender, organic solvents, for example, can also beused as auxiliary solvents. The main liquid solvents which are suitableare: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinatedaromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons such ascyclohexane or paraffins, for example petroleum fractions, mineral andvegetable oils, alcohols such as butanol or glycol as well as theirethers and esters, ketones such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, strongly polar solvents such asdimethylformamide and dimethyl sulfoxide, and water.

Suitable solid carriers are:

for example ammonium salts and ground natural minerals such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals such as highly disperse silica,alumina and silicates; suitable solid carriers for granules are: forexample crushed and fractionated natural rocks such as calcite, marble,pumice, sepiolite and dolomite, or else synthetic granules of inorganicand organic meals, and granules of organic material such as sawdust,coconut shells, maize cobs and tobacco stalks; suitable emulsifiersand/or formers are: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolyzates; suitable dispersantsare: for example lignin-sulfite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latexes, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids can be used in the formulations. Further additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compound according to the invention can be present in itscommercially available formulations and in the use forms prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphates, carbamates, carboxylates, chlorinatedhydrocarbons, phenylureas and substances produced by microorganisms,etc.

Particularly suitable mixing partners are, for example, the following:

Fungicides:

2-Aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine;2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide;2,6-dichloro-N-(4-trifluoromethylbenzyl)benzamide,(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)-acetamide;8-hydroxyquinoline sulfate;methyl-(E)-2-{2-[6-(2-cyanophenoxy)-pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate;methyl(E)-methoximino-[alpha-(o-tolyloxy)-o-tolyl]acetate;2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,benalaxyl, benodanil, benomyl, binapacryl, biphenyl, bitertanol,blasticidin-S, bromuconazole, bupirimate, buthiobate, calciumpolysulfide, captafol, captan, carbendazim, carboxin, chinomethionat(quinomethionate), chloroneb, chloropicrin, chlorothalonil,chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,dichlorophen, diclobutrazol, dichlofluanid, diclomezine, dicloran,diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole,dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine,drazoxolon, edifenphos, epoxyconazole, ethirimol, etridiazole,fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil,fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam,ferimzone, fluazinam, fludioxonil, fluoromide, fluquinconazole,flusilazole, flusulfamide, flutolanil, flutriafol, folpet,fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furmecyclox,guazatine, hexachlorobenzene, hexaconazole, hymexazol, imazalil,imibenconazole, iminoctadine, iprobenfos (IBP), iprodione,isoprothiolane, kasugamycin, copper preparations such as: copperhydroxide, copper naphthenate, copper oxychloride, copper sulfate,copper oxide, oxine-copper and Bordeaux mixture, mancopper, mancozeb,maneb, mepanipyrim, mepronil, metalaxyl, metconazole, methasulfocarb,methfuroxam, metiram, metsulfovax, myclobutanil, nickeldimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,oxadixyl, oxamocarb, oxycarboxin, pefurazoate, penconazole, pencycuron,phosdiphen, phthalide, pimaricin, piperalin, polycarbamate, polyoxin,probenazole, prochloraz, procymidone, propamocarb, propiconazole,propineb, pyrazophos, pyrifenox, pyrimethanil, pyroquilon, quintozene(PCNB), sulfur and sulfur preparations, tebuconazole, tecloftalam,tecnazene, tetraconazole, thiabendazole, thicyofen, thiophanate-methyl,thiram, tolclophos-methyl, tolylfluanid, triadimefon, triadimenol,triazoxide, trichlamide, tricyclazole, tridemorph, triflumizole,triforine, triticonazole, validamycin A, vinclozolin, zineb, ziram

Bactericides:

Bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline,probenazole, streptomycin, tecloftalam, copper sulfate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

Abamectin, AC 303 630, acephate, acrinathrin, alanycarb, aldicarb,alphamethrin, amitraz, avermectin, AZ 60541, azadirachtin, azinphos A,azinphos M, azocyclotin, Bacillus thuringiensis, bendiocarb,benfuracarb, bensultap, beta-cyfluthrin, bifenthrin, BPMC, brofenprox,bromophos A, bufencarb, buprofezin, butocarboxin, butylpyridaben,cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,CGA-157 419, CGA 184699, cloethocarb, chlorethoxyfos, chlorfenvinphos,chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,cis-resmethrin, clocythrin, clofentezine, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,diazinon, dichlofenthion, dichlorvos, dicliphos, dicrotophos, diethion,diflubenzuron, dimethoate, dimethylvinphos, dioxathion, disulfoton,edifenphos, emamectin, esfenvalerate, ethiofencarb, ethion, ethofenprox,ethoprophos, etrimphos, fenamiphos, fenazaquin, fenbutatin oxide,fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin,fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, fluazinam,flucycloxuron, flucythrinate, flufenoxuron, flufenprox, fluvalinate,fonofos, formothion, fosthiazate, fubfenprox, furathiocarb, HCH,heptenophos, hexaflumuron, hexythiazox, imidacloprid, iprobenfos,isazofos, isofenphos, isoprocarb, isoxathion, ivermectin,lambda-cyhalothrin, lufenuron, malathion, mecarbam, mevinphos,mesulfenfos, metaldehyde, methacrifos, methamidophos, methidathion,methiocarb, methomyl, metolcarb, milbemectin, monocrotophos, moxidectin,naled, NC 184, NI 25, nitenpyram, omethoate, oxamyl, oxydemethon M,oxydeprofos, parathion A, parathion M, permethrin, phenthoate, phorate,phosalone, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,pirimiphos A, profenofos, promecarb, propaphos, propoxur, prothiofos,prothoate, pymetrozin, pyraclofos, pyridaphenthion, pyresmethrin,pyrethrum, pyridaben, pyrimidifen, pyriproxyfen, quinalphos, RH 5992,salithion, sebufos, silafluofen, sulfotep, sulprofos, tebufenozide,tebufenpyrad, tebupirimphos, teflubenzuron, tefluthrin, temephos,terbam, terbufos, tetrachlorvinphos, thiafenox, thiodicarb, thiofanox,thiomethon, thionazin, thuringiensin, tralomethrin, triarathene,triazophos, triazuron, trichlorfon, triflumuron, trimethacarb,vamidothion, XMC, xylylcarb, YI 5301/5302, zetamethrin.

Herbicides:

for example anilides such as, for example, diflufenican and propanil;aryl-carboxylic acids such as, for example, dichloropicolinic acid,dicamba and picloram; aryloxyalkanoic acids such as, for example, 2,4 D,2,4 DB, 2,4 DP, fluroxypyr, MCPA, MCPP and triclopyr;aryloxy-phenoxy-alkanoic esters such as, for example, diclofop-methyl,fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl andquizalofop-ethyl; azinones such as, for example, chloridazon andnorflurazon; carbamates such as, for example, chlorpropham, desmedipham,phenmedipham and propham; chloroacetanilides such as, for example,alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlorand propachlor; dinitroanilines such as, for example, oryzalin,pendimethalin and trifluralin; diphenyl ethers such as, for example,acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen andoxyfluorfen; ureas such as, for example, chlortoluron, diuron,fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylaminessuch as, for example, alloxydim, clethodim, cycloxydim, sethoxydim andtralkoxydim; imidazolinones such as, for example, imazethapyr,imazamethabenz, imazapyr and imazaquin; nitriles such as, for example,bromoxynil, dichlobenil and ioxynil; oxyacetamides such as, for example,mefenacet; sulfonylureas such as, for example, amidosulfuron,bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron,metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfuron-ethyl,thifensulfuron-methyl, triasulfuron and tribenuron-methyl;thiocarbamates such as, for example, butylate, cycloate, di-allate,EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and tri-allate;triazines such as, for example, atrazine, cyanazine, simazine, simetryn,terbutryn and terbutylazine; triazinones such as, for example,hexazinone, metamitron and metribuzin; others such as, for example,aminotriazole, benfuresate, bentazone, cinmethylin, clomazone,clopyralid, difenzo-quat, dithiopyr, ethofumesate, fluorochloridone,glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac,sulfosate and tridiphane.

A mixture with fertilizers and growth regulators is also possible.

The active compound according to the invention can further be present inits commercially available formulations, and in the use forms preparedfrom these formulations, as a mixture with synergistic agents.Synergistic agents are compounds which increase the action of the activecompounds, without it being necessary for the synergistic agent added tobe active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms. The active compounds according to the invention can be appliedeither before or after the emergence of the plants. They can also beincorporated into the soil before sowing.

The amount of active compound used can vary within a substantial range.It depends essentially on the nature of the desired effect. In general,the amounts used are between 10 g and 10 kg of active compound perhectare of soil surface, preferably between 50 g and 5 kg per ha.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay, as well as by a good stability to alkali on limed substrates.

The active compounds according to the invention are not only activeagainst plant, hygiene and stored product pests, but also, in theveterinary medicine sector, against animal parasites (ectoparasites),such as scaly ticks, argasidae, scab mites, trombidae, flies (stingingand sucking), parasitic fly larvae, lice, hair lice, bird lice andfleas. These parasites include:

From the order of the Anoplurida, for example, Haematopinus spp.,Linognathus spp., Pediculus spp., Phtirus spp. and Solenopotes spp.

From the order of the Mallophagida and the sub-orders Amblycerina andIschnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp.,Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp.,Trichodectes spp. and Felicola spp.

From the order Diptera and the sub-orders Nematocerina and Brachycerina,for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp.,Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp.,Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopotaspp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp.,Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossinaspp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp.,Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp.,Hippobosca spp., Lipoptena spp. and Melophagus spp.

From the order of the Siphonapterida, for example, Pulex spp.,Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.

From the order of the Heteropterida, for example, Cimex spp., Triatomaspp., Rhodnius spp. and Panstrongylus spp.

From the order of the Blattarida, for example, Blatta orientalis,Periplaneta americana, Blattela germanica and Supella spp.

From the sub-class of the acaria (Acarida) and the orders of themetastigmata and mesostigmata, for example, Argas spp., Ornithodorusspp., Otabius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,Dermacentor spp., Haemaphysalis spp., Hyalomma spp., Rhipicephalus spp.,Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp.and Varroa spp.

From the order of the Actinedida (prostigmata) and Acaridida(astigmata), for example, Acarapis spp., Cheyletiella spp.,Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp.,Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp.,Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp.,Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp. and Laminosioptes spp.

By way of example, they show an outstanding activity against Luciliacuprina.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock such as, for example, cattle, sheep, goats, horses,pigs, donkeys, camels, buffalos, rabbits, chickens, turkeys, ducks,geese and bees, other pets such as, for example, dogs, cats, cage birdsand aquarium fish, and also so-called test animals such as, for example,hamsters, guinea pigs, rats and mice. By controlling these arthropods,cases of death and reductions in productivity (for meat, milk, wool,hides, eggs, honey etc.) should be diminished, so that simpler and moreeconomic animal husbandry is made possible by use of the activecompounds according to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boli, the feed-through process and suppositories, by parenteraladministration, such as, for example, by injections (intramuscular,subcutaneous, intravenous, intraperitoneal, etc.), implants, by nasaladministration, by dermal use in the form, for example, of bathing ordipping, spraying, pouring on and spotting on, washing and powdering,and also with the aid of molded articles containing the activecompounds, such as collars, ear tags, tail tags, limb bands, halters,marking devices, etc.

When used in connection with cattle, poultry, pets, etc., the activecompounds of the formula (I) can be used as formulations (for examplepowders, emulsions, flowable compositions), which contain the activecompound in an amount from 1 to 80% by weight, directly or after100-fold to 10,000-fold dilution, or they can be used as a chemicalbath.

Furthermore, it has been found that the compounds according to theinvention of the formula (I) show high insecticidal action againstinsects which destroy industrial materials.

The following insects may be mentioned as examples and preferably, butnot by way of limitation:

Beetles such as

Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobiumrufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobiusmollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctusplanicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale,Minthes rugicollis, Xyleborus spec., Tryptodendron spec., Apatemonachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylonspec. and Dinoderus minutus.

Hymenoptera such as

Sirex juvencus, Urocerus gigas, Urocerus gigas taignus and Urocerusaugur.

Termites such as

Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola,Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermeslucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis andCoptotermes formosanus.

Bristletails

such as Lepisma saccharin.

Industrial materials in the present context are understood to benon-living materials, such as, preferably, plastics, glues, sizes, paperand board, leather, wood and wood-processing products and paints.

Very particularly preferably, the materials to be protected againstinsect infestation are wood and wood-processing products.

Wood and wood-processing products which can be protected by thecomposition according to the invention or mixtures containing it areunderstood to be, for example: construction timber, wooden beams,railroad sleepers, bridge components, landing-stages, wooden vehicles,crates, pallets, containers, telephone poles, wood cladding, woodenwindows and doors, plywood, particle boards, joinery work or woodenproducts which are used quite generally in house building or joinery.

The active compounds can be used as such, in the form of concentrates orgenerally customary formulations such as powders, granules, solutions,suspensions, emulsions or pastes.

The said formulations can be produced in a manner known per se, forexample by mixing the active compounds with at least one solvent ordiluent, emulsifier, dispersant and/or binder or fixer, water-repellent,if appropriate driers and UV stabilizers and, if appropriate, dyestuffsand pigments and other processing aids.

The insecticidal compositions or concentrates used to protect wood andwooden materials contain the active compound according to the inventionin a concentration of 0.0001 to 95% by weight, in particular 0.001 to60% by weight.

The amount of the compositions or concentrates used depends on the typeand incidence of the insects and on the medium. The optimum applicationrate can be determined by test series each time in use. However, it isgenerally sufficient to use 0.0001 to 20% by weight, preferably 0.001 to10% by weight, of the active compound, based on the material to beprotected.

As solvent and/or diluent, use is made of an organic chemical solvent orsolvent mixture and/or an oily or oleaginous non-volatile organicchemical solvent or solvent mixture and/or a polar organic chemicalsolvent or solvent mixture and/or water and, if appropriate, anemulsifier and/or wetting agent.

As organic chemical solvents, use is preferably made of oily oroleaginous solvents having a relative evaporation rate greater than 35and a flashpoint above 30° C., preferably above 45° C. As non-volatile,water-insoluble, oily and oleaginous solvents of this type, use is madeof appropriate mineral oils or their aromatic fractions ormineral-oil-containing solvent mixtures, preferably white spirit,petroleum and/or alkylbenzene.

Those which are advantageously used are mineral oils having a boilingrange from 170 to 220° C., white spirit having a boiling range from 170to 220° C., spindle oil having a boiling range from 250 to 350° C.,petroleum or aromatics of boiling range from 160 to 280° C., turpentineoil and the like.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthlene, preferablyα-monochloronaphthlene, are used.

The organic non-volatile oily or oleaginous solvents having a relativeevaporation rate greater than 35 and a flashpoint above 30° C.,preferably above 45° C., can be replaced in part by readily ormedium-volatile organic chemical solvents, with the proviso that thesolvent mixture likewise has a relative evaporation rate greater than 35and a flashpoint above 30° C., preferably above 45° C., and that theinsecticide-fungicide mixture is soluble or emulsifiable in this solventmixture.

According to a preferred embodiment, some of the organic-chemicalsolvent or solvent mixture is replaced by an aliphatic polarorganic-chemical solvent or solvent mixture. Preferably, hydroxyl-and/or ester- and/or ether-group-containing aliphatic organic-chemicalsolvents such as, for example, glycol ethers, esters or the like areused.

As organic-chemical binders, in the context of the present invention,use is made of the binding drying oils and/or synthetic resins which areknown per se and are water-dilutable and/or are soluble or dispersibleor emulsifiable in the organic-chemical solvents used, in particularbinders comprising or containing an acrylic resin, a vinyl resin, forexample poly(vinyl acetate), polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin such as indene-coumarone resin,silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin employed as binder can be used in the form of anemulsion, dispersion or solution. As binder, use can also be made ofbitumen or bituminous substances up to 10% by weight. In addition,dyestuffs, pigments, water-repellent agents, reodorants and inhibitorsor anti-corrosive agents and the like.

As organic-chemical binders, preference is given according to theinvention to at least one alkyd resin or modified alkyd resin and/or adrying vegetable oil present in the composition or in the concentrate.Preferably, alkyd resins having an oil content of greater than 45% byweight, preferably 50 to 68% by weight, are used according to theinvention.

The binder mentioned can be entirely or partially replaced by a fixingagent (mixture) or a plasticizer (mixture). These additions are intendedto prevent volatilization of the active compounds or else acrystallization or precipitation. Preferably, they replace 0.01 to 30%of the binder (based on 100% of the binder used).

The plasticizers originate from the chemical classes of the phthalicesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricesters, such as tributyl phosphate, adipic esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers orhigher-molecular glycol ethers, glycerol esters and p-toluenesulfonicesters.

Fixing agents are chemically based on poly(vinyl alkyl ethers) such as,for example, poly(vinyl methyl ether) or ketones, such as benzophenoneand ethylene-benzophenone.

As solvent or diluent, water is also especially suitable, if appropriatein a mixture with one or more of the abovementioned organic-chemicalsolvents or diluents, emulsifiers and dispersants.

Particularly effective protection of wood is achieved by industrialimpregnation processes, e.g. vacuum, double vacuum or pressureprocesses.

The ready-to-use compositions can, if appropriate, contain furtherinsecticides and, if appropriate, one or more further fungicides.

Additional mixing partners which are suitable are preferably theinsecticides and fungicides mentioned in WO 94/29 268. The compoundsmentioned in this document are an explicit part of the presentapplication.

Very particularly preferred mixing partners which may be mentioned areinsecticides, such as chlorpyrifos, phoxim, silafluofen, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron and triflumuron as well as fungicides such asepoxyconazole, hexaconazole, azaconazole, propiconazole, tebuconazole,cyproconazole, metconazole, imazalil, dichlofluanid, tolylfluanid,3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one and4,5-dichloro-N-octylisothiazolin-3-one.

The preparation and use of the active compounds according to theinvention are given by the following examples.

PREPARATION EXAMPLES Example 1

6.4 g (20 mmol) of4-hydroxy-5-methyl-6-(2-pyridyl)-3-(2,4,6-trimethylphenyl)-2-pyrone in50 ml of ethyl acetate are introduced in the absence of moisture. 2.02 g(20 mmol) of triethylamine are added thereto at 20° C. and a solution of2.1 g (20 mmol) of propargyloxychloromethane in 20 ml of ethyl acetateis added dropwise at 0° C. with cooling. The mixture is further stirredfor 20 h at 20° C. and the reaction is followed by thin-layerchromatography. The solution is filtered off from the precipitatedtriethylamine hydrochloride with suction and washed with ethyl acetate.The combined mother liquors are washed twice, each time with 50 ml ofhalf-saturated common salt solution, dried over magnesium sulfate andevaporated in vacuo. 8 g of crude product are obtained. 6.4 g (82% oftheory) of5-methyl-6-(2-pyridyl)-4-propargyloxymethoxy-3-(2,4,6-trimethylphenyl)-2-pyroneare obtained as an oil by flash chromatography on 500 g of silica gel 60(35-70 μm) using toluene:acetone 20:1 as mobile phase.

¹H-NMR (CDCl₃) δ[ppm]: 8.70 (m, 1H); 7.94 (td, 1H); 7.83 (m, 1H); 7.34(m, 1H); 6.93 (s, 2H); 4.74 (s, 2H); 4.11 (d, 2H); 2.42 (t, 1H); 2.41.(s, 3H); 2.30 (s, 3H); 2.20 (s, 6H).

Example 2

7.1 g (20 mmol) of6-(4-chlorophenyl)-4-hydroxy-5-methyl-3-(2,4,6-trimethyl-phenyl)-2-pyronein 50 ml of ethyl acetate are introduced in the absence of moisture.2.02 g (20 mmol) of triethylamine are added thereto at 20° C. and asolution of 2.4 g (20 mmol) of i-butoxychloromethane in 20 ml of ethylacetate is added dropwise at 0° C. with cooling. The mixture is thenfurther stirred for 20 h at 20° C. and the reaction is followed bythin-layer chromatography. The solution is filtered off from theprecipitated triethylamine hydrochloride using suction and washed withethyl acetate. The combined mother liquors are washed twice, each timewith 50 ml of half-saturated common salt solution, dried over magnesiumsulfate and evaporated in vacuo. 8.8 g of crude product are obtained.5.6 g (63% of theory) of6-(4-chlorophenyl)-4-[(2-methyl-1-propoxy)-methoxy]-5-methyl-3-(2,4,6-trimethylphenyl)-2-pyroneare obtained as an oil by flash chromatography on 500 g of silica gel 60(35-70 μm) using toluene:acetone 50:1 as mobile phase.

¹H-NMR (CDCl₃) δ[ppm]: 7.52 (AA′BB′, 4H); 6.92 (s, 2H); 4.57 (s, 2H);3.26 (d, 2H); 2.30 (s, 3H); 2.20 (s, 6H); 2.15 (s, 3H); 1.78 (m, 1H);0.87 (d, 6H).

Examples 3-35

The compounds of the formula (I-a) which are listed in Table 1 belowwere obtained in a similar manner to Examples 1 and 2 and in accordancewith the general details for preparation.

TABLE 1 (I-a)

Physical data: m.p. Ex. or ¹H-NMR (CDCl₃): δ No. A D R¹ R² [ppm] 3 H CH₃H CH₂CH₃ 133-135° C. 4 CH₃

H CH₂CH₃ 156-158° C. 5 H CH₂CH(CH₃)₂ H CH₂CH₃ 6.91(s 2H); 6.28(s 1H);5.12(s 2H); 3.60 (q 2H); 2.42(d 2H); 2.28(s 3H); ˜2.2(m 1H); 2.10(s 6H);1.18(t 3H); 1.00(d 6H) 6

H CH₂CH₃ 6.88(s 2H); 5.00(AB 2H); 3.63(bs 1H); 3.53 (q 2H); 3.25(bs 1H);2.26(s 3H); 2.10(s 1H); 2.04(s 3H); 1.93 (m 2H); 1.81(m 1H); 1.25-1.45(m3H); 1.14 (t 3H) 7 CH₃

H CH₂C≡CH 104-106° C. 8 CH₃

H CH₂CH(CH₃)₂ 91-93° C. 9 CH₃

H CH(CH₃)₂ 77-79° C. 10 CH₃

H CH₂CH(CH₃)₂ 8.70(m 1H); 7.93(td 1H); 7.83(m 1H); 7.33 (m 1H); 6.91(s2H); 4.58(s 2H); 3.26(d 2H); 2.40(s 3H); 2.28 (s 3H); 2.18(s 6H);1.77(m, 1H); 0.86(d, 6H) 11 CH₃

H CH(CH₃)₂ 83-85° C. 12 H

H CH₂C≡CH 143-145° C. 13 H

H CH₂CH(CH₃)₂ 128-131° C. 14 H

H CH(CH₃)₂ 140-142° C. 15 —(CH₂)₄— H CH₂C≡CH 123-125° C. 16 —(CH₂)₄— HCH₂CH(CH₃)₂ 67-69° C. 17 CH₃

H CH₂C≡CH 108-110° C. 18 CH₃

H CH(CH₃)₂ 101-103° C. 19 H

H CH₂C≡CH 6.92(s 2H); 6.85(s 1H); 5.26(s 2H); 4.20 (d 2H); 2.43(t 1H);2.30(s 3H); 2.09(s 6H); 1.83(AA′ 2H); 1.51(BB′ 2H) 20 H

H CH₂CH(CH₃)₂ 94-97° C. 21 H

H CH(CH₃)₂ 6.93(s 1H); 6.91(s 2H); 5.19(s 2H); 3.85 (sp 1H); 2.28(s 3H);2.08(s 6H); 1.84(AA′ 2H); 1.51(BB′ 2H); 1.14(d 6H) 22 CH₃

H CH₂CH(CH₃)₂ 7.58(d 1H); 7.05(d 1H); 6.91(s 2H); 6.57 (dd 1H); 4.53(s2H); 3.23(d 2H); 2.23(s 3H); 2.28(s 3H); 2.17 (s 6H); 1.76(m 1H); 0.87(d6H) 23 CH₃ C(CH₃)₃ H CH₂CH(CH₃)₂ 6.89(s 2H); 4.47(s 2H); 3.20(d 2H);2.28 (s 3H); 2.14(s 6H); 1.75 8m 1H); 1.43(s 9H); 0.85(d 6H) 24 CH₃ H HCH(CH₃)₂ 57-59° C. 25 H CH═CH(CH₃)₂ H CH(CH₃)₂ 6.91(s 2H); 6.32(s 1H);5.90(bs 1H); 5.13 (s 2H); 3.85(sp 1H); 2.30(s 3H); 2.21(s 3H); 2.10(s6H); 1.97 (s 3H); 1.13(d 6H) 26 CH₃

H CH₂CH₃ 124-125° C. 27 CH₃

H CH₂CH(CH₃)₂ 7.70(AB 2H); 7.18(X 1H); 6.91(s 2H); 4.55 (s 2H); 3.21(d2H); 2.61(s 3H); 2.37(s 3H); 2.28(s 3H); 2.16 (s 6H); 1.78(m 1H); 0.85(d6H) 28 CH₃

H CH(CH₃)₂ 94-95° C. 29 CH₃

H CH₂C≡CH 6.88(s 2H); 4.64(s 2H); 4.12(d 2H); 2.38 (t 1H); 2.25(s 3H);2.12 (2s 3+3H); 2.03(s 3H); 1.92(m 1H); 1.50(s 3H); 1.42(m 1H) 30 CH₃

H CH₂CH(CH₃)₂ 6.90(s 2H); 4.50(AB 2H); 3.22(d 2H); 2.26 (s 3H); 2.12(s3H); 2.11(s 3H); 2.02(s 3H); 1.93(m 1H); 1.77 (m 1H); 1.51(s 3H); 1.43(m1H); 0.85 (d 6H) 31 CH₃

H CH(CH₃)₂ 6.88(s 2H); 4.52(AB 2H); 3.75(sp 1H); 2.26 (s 3H); 2.11(2s3+3H); 2.01(s 3H); 1.92(m 1H); 1.50(s 3H); 1.41 (m 1H); 1.11(2d 3+3H) 32CH₃

H CH₂CH₃ 65-68° C. 33 CH₃

H CH₂C≡CH 6.88(s 2H); 4.62(s 2H); 4.09(d 2H); 3.16 (m 1H); 2.40(t 1H);2.25(s 3H); 2.13(s 6H); 2.02(s 3H); 1.8- 1.95(m 6H); 1.6-1.7(m 2H) 34CH₃

H CH(CH₃)₂ 6.88(s 2H); 4.50(s 2H); 3.72(sp 1H); 3.15 (m 1H); 2.27(s 3H);2.13(s 6H); 2.01(s 3H); 1.8-1.95(m 6H); 1.6-1.7(m 2H); 1.10(d 6H) 35 CH₃

H CH₂CH(CH₃)₂ 6.88(s 2H); 4.47(s 2H); 3.20(d 2H); 3.18 (m 1H); 2.25(s3H); 2.12(s 6H); 2.01(s 3H); 1.8-1.95(m 6H); 1.74(m 1H); 1.6-1.7(m 2H);0.83(d 6H)

Example 36

2-[(2-Methyl-1-propoxy)-methoxy]-5-methyl-6-(3-thienyl)-3-(2,4,6-trimethyl-phenyl)-4-pyronemelting at 102-104° C. was obtained in a similar manner to Example 1from 4-hydroxy-5-methyl-6-(3-thienyl)-3-(2,4,6-trimethylphenyl)-2-pyroneand i-butoxychloromethane.

Examples 37-43

The compounds of the formula (I-b) which are listed in Table 2 belowwere obtained in a similar manner to Examples 1 and 2 and in accordancewith the general details on preparation.

TABLE 2 (l-b)

Physical data: m.p. Ex. or ¹H-NMR No. A D X Y Z_(n) R² (CDCl₃): δ [ppm]37 CH₃

CH₃ CH₃ 6-OCH₃ CH₂CH₃ 116-118° C. 38 CH₃

CH₃ CH₃ 5-CH₃ CH₂C≡CH 8.70(m 1H); 7.92(m 1H); 7.82(m 1H); 7.32(m 1H);7.04(s 1H); 7.01(s 1H); 4.76 (AB 2H); 4.11(d 2H); 2.40(t 1H); 2.39(s3H); 2.23(s 3H); 2.21 (s 3H); 2.19(s 3H); 39 CH₃

CH₃ CH₃ 5-CH₃ CH₂CH₃ 8.70(m 1H); 7.92(m 1H); 7.82(m 1H); 7.33(m 1H);7.03(s 1H); 7.01(s 1H); 4.62 (AB 2H); 3.55(q 2H); 2.40(s 3H); 2.22(s3H); 2.21(s 3H); 2.19 (s 3H); 1.12(t 3H) 40 CH₃

CH₃ CH₃ 5-CH₃ CH₂CH₃ 6.98(s 1H); 6.92(s 1H); 4.54(AB 2H); 3.51(q 2H);3.14(m 1H); 2.21(s 3H); 2.19 (s 3H); 2.15(s 3H); 2.01(s 3H); 1.80-1.95(m 6H); 1.55-1.70(m 2H); 1.12(q 3H) 41 CH₃

CH₃ Br 6-CH₃ CH₂CH₃ 132-134° C. 42 CH₃

CH₃ CH₃ 5-CH₃ CH₂— CH(CH₃)₂ 8.70(m 1H); 7.92(m 1H); 7.82(m 1H); 7.33(m1H); 7.03(s 1H); 7.01(s 1H); 4.62 (AB 2H); 3.23(d 2H); 2.40(s 3H);2.24(s 3H); 2.22(s 3H); 2.20 (s 3H); 0.75(m 1H); 0.84(d 3H) 43 CH₃

CH₃ CH₃ 6-OCH₃ CH₂CH₃ 101-103° C.

Continuation of Table 1: Physical data: m.p. or ¹H-NMR Ex. (CDCl₃): δNo. A D R¹ R² [ppm] 44 —(CH₂)₄— H CH(CH₃)₂ 6.85(s, 2H); 4.47(s, 2H);3.73(sp, 1H); 1.10(d, 6H) 45 —C(CH₃)₂OC(CH₃)₂— H CH₂CH₃ 112-115° C. 46—C(CH₃)₂OC(CH₃)₂— H CH(CH₃)₂ 94-96° C. 47 —C(CH₃)₂OC(CH₃)₂— HCH₂CH(CH₃)₂ 146-148° C. 48 —C(CH₃)₂OC(CH₃)₂— H CH₂C≡CH 102-104° C. 49CH₃

H CH₂CH₃ 8.00(s, 1H); 6.93(s, 2H); 4.60(s, 2H); 4.37(t, 2H); 3.57(q, 2H)50 CH₃

H CH(CH₃)₂ 8.00(s, 1H); 6.93(s, 2H); 4.60(s, 2H); 4.45(q, 2H); 3.78(sp,1H); 1.12(d, 6H)

Continuation of Table 2: Physical data: m.p. or ¹H-NMR Ex. (CDCl₃): δNo. A D X Y Z_(n) R² [ppm] 51 CH₃

CH₃ F H CH₂CH(CH₃)₂ 8.97(d, 1H); 7.93(d, 1H); 7.83(dt, 1H); 2.40(s, 3H);2.28(s, 3H); 0.84(d, 6H) 52 CH₃

CH₃ F H CH₂CH₃ 4.63(AB, 2H); 2.40(s, 3H); 2.26(s, 3H); 1.13(t, 3H) 53CH₃

CH₃ Cl H CH₂CH₃ 4.60(AB, 2H); 2.28(s, 3H); 2.13(s, 3H); 1.13(t, 3H) 54CH₃

CH₃ Cl H CH₂C≡CH 4.73(AB, 2H); 4.60(d, 2H); 2.42(t, 1H); 2.27(s, 3H);2.13(s, 3H) 55 CH₃

CH₃ Cl H CH₂CH(CH₃)₂ 89-91° C. 56 CH₃

CH₃ Cl H CH(CH₃)₂ 4.63(AB, 2H); 2.26(s, 3H); 2.13(s, 3H); 1.10(dd, 6H)57 CH₃

CH₃ OCH₃ H CH₂CH(CH₃)₂ 8.67(d, 1H); 7.90(d, 1H); 4.60(AB, 2H); 3.80(s,3H); 2.40(s, 3H); 2.26(s, 3H); 0.85(d, 6H) 58 CH₃

CH₃ OCH₃ H CH₂CH₃ 8.66(d, 1H); 7.93(d, 1H); 4.60(AB, 2H); 3.83(s, 3H);2.40(s, 3H); 2.27(s, 3H); 1.13(dd, 6H) 59 CH₃

CH₃ OCH₃ H CH₂CH(CH₃)₂ 4.60(AB, 2H); 3.80(s, 3H); 2.26(s, 3H); 2.12(s,3H); 0.85(d, 6H) 60 CH₃

CH₃ OCH₃ H CH₂CH₃ 4.62(AB, 2H); 3.80(s, 3H); 2.27(s, 3H); 2.13(s, 3H);1.17(t, 3H)

Use Examples Example A

Phaedon Larvae Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with mustard beetle larvae (Phaedon cochleariae), while theleaves are still moist.

After the specified period of time, the destruction in % is determined.100% means that all the beetle larvae have been killed; 0% means thatnone of the beetle larvae have been killed.

In this test, the compounds according to Preparation Examples 4, 5, 9,26, 27, 28 and 31, for example, showed a degree of destruction of 100%after 7 days at an exemplary active compound concentration of 0.01%.

Example B

Plutella Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with caterpillars of the diamond-back moth (Plutellamaculipennis), while the leaves are still moist.

After the specified period of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, the compounds according to Preparation Examples 4, 5, 9,10, 18, 27, 28, 31, 32 and 34, for example, showed a degree ofdestruction of 100% after 7 days at an exemplary active compoundconcentration of 0.1%.

Example C

Spodoptera Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with caterpillars of the owlet moth (Spodoptera frugiperda),while the leaves are still moist.

After the specified period of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, the compounds according to Preparation Examples 4, 5, 9,32 and 34, for example, showed a degree of destruction of 100% after 7days at an exemplary active compound concentration of 0.1%.

Example D

Nephotettix Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Rice seedlings (Oryzae sativa) are treated by being dipped into thepreparation of the active compound of the desired concentration and areinfested with larvae of the green rice leafhopper (Nephotettixcincticeps), while the seedlings are still moist.

After the specified period of time, the destruction in % is determined.100% means that all the leafhoppers have been killed; 0% means that noneof the leafhoppers have been killed.

In this test, the compounds according to Preparation Examples 1, 4, 7,9, 11, 18, 21, 26, 27, 28, 29, 30, 31, 32 and 33, for example, showed adegree of destruction of 100% after 6 days at an exemplary activecompound concentration of 0.1%.

Example E

Myzus Test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) which are highly infested by thepeach aphid (Myzus persicae) are treated by being dipped into thepreparation of the active compound of the desired concentration.

After the specified period of time, the destruction in % is determined.100% means that all the aphids have been killed; 0% means that none ofthe aphids have been killed.

In this test, the compounds according to Preparation Examples 1, 9, 11,26, 27, 31, 32 and 36, for example, showed a degree of destruction of 95to 100% after 6 days at an exemplary active compound concentration of0.1%.

Example F

Limit Concentration Test/Root-systemic Action

Test insect: Aphis fabae

Solvent: 4 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is intimately mixed with soil. Theconcentration of the active compound in the preparation is of noimportance in practise, only the amount by weight of active compound perunit volume of soil, which is given in ppm (=mg/l), being decisive. Thetreated soil is transferred into pots and these are planted with beans(Vicia faba). The active compound can in this way be taken up from thesoil by the roots of the plants and be transported into the leaves.

To demonstrate the root-systemic effect, the leaves only are infestedwith black bean aphids (Aphis fabae) after 7 days. After a further 2days, the evaluation is made by counting or estimating the dead animals.The root-systemic action of the active compound is deduced from thedestruction figures. It is 100% if all test animals have been killed and0% if just as many test insects are still alive as in the case of theuntreated control.

In this test, the compounds according to Preparation Examples 1, 10 and11, for example, showed a degree of destruction of 100% at an examplaryactive compound concentration of 20 ppm.

Example G

Tetranychus Test (Resistance)

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Bean plants (Phaseolus vulgaris) which are highly infested by alldevelopment stages of the common spider mite (Tetranychus urticae) aretreated by being dipped into the preparation of active compound of thedesired concentration.

After the specified period of time, the destruction in % is determined.100% means that all the spider mites have been killed 0% means that noneof the spider mites have been killed.

In this test, the compounds according to Preparation Examples 9, 10, 11,21 and 30, for example, gave a degree of destruction of 100% after 13days at an exemplary active compound concentration of 0.01%.

Example H

Sphaerotheca Test (Cucumber)/Protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are dusted with conidia of the fungusSphaerotheca fuliginea.

The plants are then placed in a greenhouse at 23 to 24° C. and at arelative atmospheric humidity of about 75%.

Evaluation is carried out 10 days after the inoculation.

In this test, the compounds according to Preparation Examples1,2,4,7,8,9,10,11,17,18 and 21, for example, showed an activity of 100%in comparison with the untreated control at an exemplary active compoundconcentration of 100 ppm.

Example I

Venturia Test (Apple)/Protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous conidiasuspension of the apple scab causative organism (Venturia inaequalis)and then remain in an incubation cabin at 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then. placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

In this test, the compounds according to Preparation Examples 4, 9 and18, for example, showed an activity of 95-99% in comparison with theuntreated control at an exemplary active compound concentration of 100ppm.

Example J

Botrytis Test (Bean)/Protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, 2 small pieces of agar covered with Botrytiscinerea are placed on each leaf. The inoculated plants are placed in adarkened humid chamber at 20° C. 3 days after the inoculation, the sizeof the infected spots on the leaves is evaluated.

In this test, the compounds according to Preparation Examples 4, 9 and18, for example, showed an activity of 94-99% in comparison with theuntreated control at an exemplary active compound concentration of 500ppm.

Example K

Pyricularia Test (Rice)/Protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier tothe desired concentration.

To test for protective activity, young rice plants are sprayed with thepreparation of active compound until dripping wet. 4 days after thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Pyricularia oryzae. The plants are then placed in agreenhouse at 100% relative atmospheric humidity and 25° C.

Evaluation of the disease infestation is carried out 4 days after theinoculation. In this test, the compounds according to PreparationExamples 4, 5, 8, 9, 10, 11 and 18, for example, showed an activity of70-100% in comparison with the untreated control at an exemplary activecompound concentration of 0.05%.

Example L

Test with Fly Larvae/Development-inhibiting Activity

Test animals: All larval stages of Lucilia cuprina (OP resistant) [Pupaeand adults (without contact with the active compound)]

Solvent: 35 parts by weight of ethylene glycol monomethyl ether 35 partsby weight of nonylphenol polyglycol ether

To produce a suitable formulation, 3 parts by weight of active compoundare mixed with 7 parts of the solvent/emulsifier mixture specified aboveand the emulsion concentrate thus obtained is diluted with water to thedesired concentration in each case.

For each concentration, 30 to 50 larvae are introduced into test tubescontaining horse meat (1 cm³), onto which 500 ml of the dilution undertest are pipetted. The glass test tubes are placed in plastic beakerswhich have bottoms covered with sea sand and are kept in anair-conditioned room (26° C.±1.5° C., 70% relative humidity ±10%). Theaction is inspected after 24 hours and 48 hours (larvicidal action).After emigration of the larvae (approximately 72 h), the test tubes areremoved and perforated plastic lids are placed on the beakers. After 1½times the development period (emergence of the control flies), theemerged flies and the pupae/pupal cases are counted.

The criterion of activity used is the occurrence of death of the treatedlarvae after 48 h (larvicidal effect), or the inhibition of adultemergence from the pupae, or inhibition of pupal formation. Thecriterion used for the in-vitro activity of a substance is inhibition offly development, or cessation of development prior to the adult stage.100% larvicidal activity means that all larvae have died after 48 hours.100% development inhibition activity means that no adult flies emerged.

In this test, the compounds according to Preparation Examples 1, 4, 9,10, 11 and 18, for example, had an activity of 100% at an exemplaryactive compound concentration of 1000 ppm.

What is claimed is:
 1. A compound of the formula (I):

in which X represents fluorine, chlorine, bromine, iodine, nitro, cyano,C₁-C₈-alkyl, C₂-C₆-alkenyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy,C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl, C₁-C₆-alkylsulfonyl; C₁-C₆-alkyl,C₂-C₆-alkenyl C₁-C₆-alkoxy or C₂-C₆-alkenyloxy, each of which issubstituted by fluorine, chlorine or bromine; or phenyl, phenoxy,phenylthio, benzyloxy or benzylthio, each of which is optionallysubstituted by fluorine, chlorine, bromine, iodine, nitro, cyano or byC₁-C₆-alkyl or C₁-C₆-alkoxy, each of which is optionally substituted byfluorine, chlorine or bromine, Y represents hydrogen, fluorine,chlorine, bromine, iodine, nitro, cyano, C₁-C₈-alkyl, C₂-C₆-alkenyl,C₁-C₆-alkoxy, C₂-C₆-alkenyloxy, C₁-C₆-alkylthio, C₁-C₆-alkylsulfinyl,C₁-C₆-alkylsulfonyl; or C₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₆-alkoxy orC₂-C₆-alkenyloxy, each of which is substituted by fluorine, chlorine orbromine, Z represents fluorine, chlorine, bromine, iodine, nitro, cyano,C₁-C₈-alkyl, C₂-C₆-alkenyl, C₁-C₆-alkoxy, C₂-C₆-alkenyloxy orC₁-C₆-alkyl, C₂-C₆-alkenyl, C₁-C₆-alkoxy or C₂-C₆-alkenyloxy each ofwhich is substituted by fluorine, chlorine or bromine, n represents oneof the numbers 0, 1, 2 or 3, A represents hydrogen, fluorine, chlorine,bromine or iodine; a radical, selected from the group consisting ofC₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl, C₃-C₁₀-alkenyl and C₃-C₁₀-alkinyl,which radical is optionally substituted by fluorine, chlorine, bromineor iodine; a radical selected from the group consisting of phenyl,naphthyl, and phenyl-C₁-C₆-alkyl, which radical is optionallysubstituted by fluorine, chlorine, bromine, iodine, nitro, C₁-C₈-alkyl,C₁-C₈-alkoxy, C₁-C₈-alkylthio, C₁-C₈-halogenoalkyl, C₁-C₈-halogenoalkoxyor cyano; or one of the groups —COR³, —CO₂R³, —CN, —CONR³R⁴, —SO₂R³ or—P(O)(OR³)OR⁴, in which R³ and R⁴ independently of one another representhydrogen; C₁-C₁₀-alkyl or C₃-C₁₀-alkenyl, each of which is optionallysubstituted by fluorine, chlorine, bromine or iodine; or a radicalselected from the group consisting of phenyl, naphthyl, andphenyl-C₁-C₆-alkyl which radical is optionally substituted by fluorine,chlorine, bromine, iodine, nitro, C₁-C₈-alkyl, C₁-C₈-alkoxy,C₁-C₈-alkylthio, C₁-C₈-halogenoalkyl, C₁C₈-halogenoalkoxy or cyano, or Drepresents hydrogen; C₁-C₁₂-alkyl, C₃-C₈-alkenyl, C₃-C₈-alkinyl,C₁-C₁₀-alkoxy-C₂-C₈-alkyl, poly-C₁-C₈-alkoxy-C₂-C₈-alkyl orC₁-C₁₀-alkylthio-C₂-C₈-alkyl, each of which is optionally substituted byfluorine, chlorine, bromine or iodine; cyano-, C₁-C₈-alkyloxycarbonyl-or C₁-C₈-alkylcarbonyloxy-substituted C₁-C₁₂-alkyl; C₃-C₈-cycloalkyl,which is optionally substituted by halogen, C₁-C₄-alkyl, C₁-C₄-alkoxy orC₁-C₄-halogenoalkyl and in which one or two not directly adjacentmethylene groups are optionally replaced by oxygen and/or sulfur; orphenyl, phenyl-C₁-C₆-alkyl, each of which is optionally substituted byhalogen, C₁-C₆-alkyl, C₁-C₆-halogenoalkyl, C₁-C₆-alkoxy,C₁-C₆-halogenoalkoxy, cyano or nitro, or A and D together represent aC₂-C₇-alkylene or C₂-C₇-alkenylene group, each of which is optionallysubstituted by C₁-C₈-alkyl, fluorine, chlorine, bromine or iodine and inwhich two carbon atoms are optionally joined by a C₁-C₂-alkylene group,R¹ represents hydrogen or C₁-C₈-alkyl, which is optionally substitutedby fluorine, chlorine, bromine or iodine and R² represents C₁-C₁₀-alkyl,C₃-C₁₀-alkenyl or C₃-C₁₀alkinyl, each of which is optionally substitutedby fluorine, chlorine, bromine or iodine.
 2. The compound of the formula(I) according to claim 1, in which X represents fluorine, chlorine,bromine, nitro, cyano, C₁-C₆-alkyl, C₂-C₄-alkenyl, C₁-C₄-alkoxy,C₂-C₄-alkenyloxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl,C₁-C₄-alkylsulfonyl; C₁-C₄-alkyl, C₂-C₄-alkenyl, C₁-C₄-alkoxy orC₂-C₄-alkenyloxy, each of which is substituted by fluorine or chlorine;or phenyl, phenoxy, phenylthio, benzyloxy or benzylthio, each of whichis optionally substituted by fluorine, chlorine, bromine, nitro or cyanoor by C₁-C₄-alkyl or C₁-C₄-alkoxy, each of which is optionallysubstituted by fluorine or chlorine, Y represents hydrogen, fluorine,chlorine, bromine, nitro, cyano, C₁-C₆-alkyl, C₂-C₄-alkenyl,C₁-C₄-alkoxy, C₂-C₄-alkenyloxy, C₁-C₄-alkylthio, C₁-C₄-alkylsulfinyl,C₁-C₄-alkylsulfonyl; or C₁-C₄-alkyl or C₁-C₄-alkoxy, each of which issubstituted by fluorine or chlorine, Z represents fluorine, chlorine,bromine, nitro, cyano, C₁-C₆-alkyl, C₁-C₄-alkoxy, C₂-C₄-alkenyloxy; orC₁-C₄-alkyl or C₁-C₄-alkoxy, each of which is substituted by fluorine orchlorine, n represents one of the numbers 0, 1 or 2, A representshydrogen, fluorine, chlorine or bromine; a radical selected from thegroup consisting of C₁-C₈-alkyl, C₃-C₈-cycloalkyl, C₃-C₈-alkenyl andC₃-C₈-alkinyl, which radical is optionally substituted by fluorine,chlorine or bromine; a radical selected from the group consisting ofphenyl, naphthyl, phenyl-C₁-C₄-alkyl, which radical is optionallysubstituted by fluorine, chlorine, bromine, nitro, C₁-C₄-alkyl,C₁-C₄-alkoxy, C₁-C₄-alkythio, C₁-C₄-halogenoalkyl, C₁-C₄-halogenoalkoxyor cyano; or one of the groups —COR³, —CO₂R³, —CN, —CONR³R⁴, —SO₂R³ or—P(O)(OR³)OR⁴, in which R³ and R⁴ independently of one another representhydrogen; C₁-C₈-alkyl or C₃-C₈-alkenyl, each of which is optionallysubstituted by fluorine, chlorine or bromine; or a radical selected fromthe group consisting of phenyl, phenyl-C₁-C₄-alkyl, which radical isoptionally substituted by fluorine, chlorine, bromine, nitro,C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-halogenoalkyl,C₁-C₄-halogenoalkoxy or cyano, or D represents hydrogen; C₁-C₁₀-alkyl,C₃-C₆-alkenyl, C₃-C₆-alkinyl, C₁-C₈-alkoxy-C₂-C₆-alkyl,poly-C₁-C₆-alkoxy-C₂-C₆-alkyl or C₁-C₈-alkylthio-C₂-C₆-alkyl, each ofwhich is optionally substituted by fluorine or chlorine; C₁-C₈-alkylwhich is substituted by cyano, C₁-C₆-alkoxycarbonyl orC₁-C₆-alkylcarbonyloxy; C₃-C₇-cycloalkyl which is optionally substitutedby fluorine, chlorine, C₁-C₄-alkyl, C₁-C₄-alkoxy or C₁-C₂-halogenoalkyl,and in which one or two non-directly adjacent methylene groups areoptionally replaced by oxygen and/or sulfur; or phenyl, orphenyl-C₁-C₄-alkyl, each of which is optionally substituted by fluorine,chlorine, bromine, C₁-C₄-alkyl, C₁-C₄-halogenoalkyl, C₁-C₄-alkoxy,C₁-C₄-halogenoalkoxy, cyano or nitro, or A and D together represent aC₂-C₆-alkylene or C₂-C₆-alkenylene group, each of which is optionallysubstituted by C₁-C₄-alkyl, fluorine, chlorine or bromine, in which twocarbon atoms are optionally connected by a C₁-C₂-alkylene group, R¹represents hydrogen or C₁-C₄-alkyl which is optionally substituted byfluorine, chlorine or bromine and R² represents C₁-C₈-alkyl,C₃-C₈-alkenyl or C₃-C₈-alkinyl, each of which is optionally substitutedby fluorine, chlorine or bromine.
 3. The compound of the formula (I)according to claim 1, in which X represents fluorine, chlorine, bromine,nitro, cyano, methyl, ethyl, n- or i-propyl, n-, s-, i- or t-butyl,vinyl, allyl, methallyl, methoxy, ethoxy, n- or i-propoxy, allyloxy,methallyloxy, trifluoromethyl, difluoromethoxy, trifluoromethoxy,trifluoroethoxy, methylthio, methylsulfinyl or methylsulfonyl, Yrepresents hydrogen, fluorine, chlorine, bromine, nitro, cyano, methyl,ethyl, n- or i-propyl, n-, s-, i- or t-butyl, methoxy, ethoxy, n- ori-propoxy, allyloxy, methallyloxy, trifluoromethyl, difluoromethoxy,trifluoromethoxy, trifluoroethoxy, methylthio, methylsulfinyl ormethylsulfonyl, Z represents fluorine, chlorine, bromine, nitro, cyano,methyl, ethyl, n- or i-propyl, n-, s-, i- or t-butyl, methoxy, ethoxy,n- or i-propoxy, allyloxy, methallyloxy, trifluoromethyl,difluoromethoxy, trifluoromethoxy or trifluoroethoxy, n representseither of the numbers 0 or 1, A represents hydrogen, fluorine, chlorineor bromine; a radical selected from the group consisting of C₁-C₆-alkyl,C₃-C₆-cycloalkyl, C₃-C₆-alkenyl and C₃-C₆-alkinyl, which radical isoptionally substituted by fluorine or chlorine; phenyl, or benzyl, eachof which is optionally substituted by fluorine, chlorine, bromine,methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy, trifluoromethyl,trifluoro-methoxy, cyano or nitro; or one of the groups —COR³, —CO₂R³,—CN, —CONR³R⁴, —SO₂R³ or —P(O)(OR³)OR⁴, in which R³ and R⁴ independentlyof one another represent hydrogen; C₁-C₆-alkyl or C₃-C₆-alkenyl, each ofwhich is optionally substituted by fluorine or chlorine; or phenyl whichis optionally substituted by fluorine, chlorine, bromine, nitro,C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-alkylthio, C₁-C₄-halogenoalkylC₁-C₄-halogenoalkoxy or cyano, or D represents hydrogen; C₁-C₈-alkyl,C₃-C₄-alkenyl, C₃-C₄-alkinyl, C₁-C₆-alkoxy-C₂-C₄-alkyl,poly-C₁-C₄-alkoxy-C₂-C₄-alkyl or C₁-C₄-alkylthio-C₂-C₄-alkyl, each ofwhich is optionally substituted by fluorine or chlorine; orC₃-C₆-cycloalkyl which is optionally substituted by fluorine, chlorine,methyl or ethyl and in which one or two non-directly adjacent methylenegroups are optionally replaced by oxygen and/or sulfur; or phenyl, orbenzyl, each of which is optionally substituted by fluorine, chlorine,bromine, methyl, ethyl, n-propyl, iso-propyl, methoxy, ethoxy,trifluoromethyl, trifluoromethoxy, cyano or nitro, or A and D togetherrepresent one of the groups —(CH₂)₃, —(CH₂)₄, —(CH₂)₅—,—CH₂—CH(CH₃)(CH₂)₂— or

R¹ represents hydrogen; or methyl or ethyl, each of which is optionallysubstituted by fluorine or chlorine and R² represents methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, allyl, methallyl, butenyl, propargylor butinyl, each of which is optionally substituted by fluorine orchlorine.